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Electrochemical Hydrogenation of CO on Cu(100): Insights from Accurate Multiconfigurational Wavefunction Methods
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2022-10-28 , DOI: 10.1021/acs.jpclett.2c02444
Qing Zhao 1 , John Mark P Martirez 2 , Emily A Carter 2, 3
Affiliation  

Copper (Cu) remains the most efficacious electrocatalyst for electrochemical CO2 reduction (CO2R). Its activity and selectivity are highly facet-dependent. We recently examined the commonly proposed rate-limiting CO hydrogenation step on Cu(111) via embedded correlated wavefunction (ECW) theory and demonstrated that only this higher-level theory yields predictions consistent with potential-dependent experimental kinetics. Here, to understand the differing activities of Cu(111) and Cu(100) in catalyzing CO2R, we explore CO hydrogenation on Cu(100) using ECW theory. We predict that the preferred pathway involves the reduction of adsorbed CO (*CO) to *COH via proton-coupled electron transfer (PCET) at working potentials, although *CHO also may form with a kinetically accessible but higher barrier. In contrast, our earlier work on Cu(111) concluded that *COH and *CHO formation via PCET are equally feasible. This work illustrates one possible origin of the facet dependence of CO2R mechanisms and products on Cu electrodes and sheds light on how the selectivity of CO2R electrocatalysts can be controlled by the surface morphology.

中文翻译:

CO 在 Cu(100) 上的电化学氢化:来自精确多构型波函数方法的见解

铜 (Cu) 仍然是最有效的电化学 CO 2还原 (CO 2 R) 电催化剂。其活性和选择性高度依赖于面。我们最近通过嵌入式相关波函数 (ECW) 理论研究了通常提出的 Cu(111) 上限速 CO 加氢步骤,并证明只有这种更高层次的理论才能产生与电位依赖性实验动力学一致的预测。在此,了解 Cu(111) 和 Cu(100) 在催化 CO 2中的不同活性R,我们使用 ECW 理论探索 Cu(100) 上的 CO 加氢反应。我们预测,首选途径涉及在工作电位下通过质子耦合电子转移 (PCET) 将吸附的 CO (*CO) 还原为 *COH,尽管 *CHO 也可能形成动力学可及但更高的势垒。相比之下,我们早期对 Cu(111) 的研究得出结论,通过 PCET 形成 *COH 和 *CHO 同样可行。这项工作说明了 CO 2 R 机制和产物对 Cu 电极的小平面依赖性的一种可能起源,并阐明了 CO 2 R 电催化剂的选择性如何通过表面形态来控制。
更新日期:2022-10-28
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